Cooperative processes in polar ordered polymers lead to departures from gas law behavior during thermo-poling. Two non-liquid crystalline dipolar polymer systems are presented to exemplify these ideas. In the first system, 'rigid V'-shaped polymer segments containing dipolar groups may be required to re-orient concertedly in a chain to achieve lower dipolar symmetry. In the second system, a cooperative reorientation process between guest molecules and an amorphous electret polymer host is facilitated through hydrogen bonding interactions. This latter system displays orientational stability comparable to some covalent bonded side- chain polymers.